Seed protectant compositions containing mixtures of 3,3,4,4-tetrachlorotetrahydrothiophene with other fungicides



United States Patent Oifice 3,461,209 Patented Aug. 12, 1969 Int. Cl.A01n 21/00, 9/12 U.S. Cl. 424-274 13 Claims ABSTRACT OF THE DISCLOSURESeed protectant composition containing, as the active ingredients, amixture of (A) 3,3,4,4-tetrachlorotetrahydrothiophene-l,1-dioxide with(B) pentachloronitrobenzene, tetrachloronitrobenzene,tetramethylthiuramdisulfide, N trichloromethylmercaptotetrahydrophthalimide, hexachlorobenzene, manganeseethylene-bis-dithiocarbamate, zinc ethylene-bis-dithiocarbamate or acombination thereof, components A and B being present in a weight ratioof 1:1 to 1:10.

This application is a continuation-in-part of application Ser. No.483,314 filed Aug. 27, 1965, now abandoned.

The present invention relates to mercury-free seed treating agents.

For protecting against various fungus diseases, for example Tilletiacaries, Fusarium disease or Rhizoktonia solani, seeds are nowadaysgenerally treated with mercurycontaining preparations. Because of theobjectionable toxicological properties of such preparations, especiallyof organic mercury compounds also used for seed treatment, attempts havebeen made to develop mercury-free seed treating agents. The compoundsand combinations hitherto proposed have the disadvantage, however, thatthey are effective only against part of the fungi concerned. Moreover,many of these compounds cause damage to the embryos which lead toconsiderable crop losses. In German Patent 1,140,392, for example,3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide has been described asan effective compound for soil and seed treatment in pea cultivation(cf. also U.S. Patent 2,957,887). When this compound was used fortreating cereals, for example wheat and barley, it has been found,however, that its phytotoxicity is too high in the range ofconcentration in which it is fully effective so that it cannot be usedin practice as a so-called universal seed protectant.

The present invention provides seed protectants containing as activesubstance a combination of3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, in a ratio by weightwithin the range of 1:1 to 1:10, with pentachloronitrobenzene and/ ortetrachloronitrobenzene and/ or tetramethylthiuramdisulphide and/orN-trichloromethylmercaptotetrahydrophthalimide and/or hexachlorobenzene,and/or a manganese++ or zinc++ salt of ethylene-bis-dithiocarbamic acid.

The following examples illustrate the invention but they are notintended to limit it thereto, the parts being by weight.

As shown in the examples, the above combinations have a stronger actionon the fungi than the individual constituents. The active substancecombinations are applied in admixture with an inert substance.

EXAMPLE 1 Winter wheat infested with T illetia tritici was treated witha preparation A containing as active substance 5 parts 3,3,4,4tetrachlorotetrahydrothiophene dioxide combined with 15 partspentachloronitrobenzene and parts talcum as inert material.

For comparison there were used a preparation B containing as activesubstance 20 parts tetrachlorotetrahydrothiophene dioxide alone and 80parts talcum as inert material and a preparation C containing as activesubstance 20 parts pentachloronitrobenzene alone and 80 parts talcum asinert material A commercial seed protectant containing 2% of mercury wasused as comparison preparation D. Each formulated preparation wasapplied in a concentration of g., 50 g. and 25 g., respectively, for 100kg. of seed grains. The treatment was carried out in a conventionaldrum.

One day after the treatment, the seed grains were sown in lots of 2 m.each with 5 repetitions. On harvesting, the sound ears and thoseinfested with Tilletia tritici were counted and the figures so obtainedwere compared with those obtained in untreated control plants.

The results set forth in the following Table 1 show that combination Aconsisting of 3,3,4,4-tetrachlorotetrahydrothiophene-l,l-dioxide andpentachloronitrobenzene is not only superior to individual constituentsB and C but also to the commercial mercury-containing product D in thelow concentrations. Table 1 also shows that the plants were not damagedby preparation A whereas pronounced to strong phytotoxic symptoms wereproduced by preparation B.

TABLE 1 plants with Preparation 100 g./100 kg. 50 g./l00 kg. 25 g./100kg. 100 g./100 kg.

Damages to plants: 0=no damage, 5=plants died down.

EXAMPLE 2 Oats strongly infested artificially with Ustilago avenae(loose smut of oats) were treated with a preparation A containing asactive substance 10 parts of3,3,4,4-tetrachlorotetrahydrothiophene-1,l-dioxide combined with 20parts of tetramethylthiuram disulphide (TMTD) and 70 parts of talcum asinert substance.

For comparison there were used a preparation B which contained as activesubstance 20 parts (higher concentrations cause too much damage to theplants) of 3,3,4,4- tetrachlorotetrahydrothiophene-1,1-dioxide with 80parts of talcum as inert material, and a preparation C containing asactive substance 30 parts of TMTD alone in addition to 70 parts oftalcum. Furthermore, a commercial preparation containing 2% of mercurywas used as comparison preparation D.

The seed grains were treated for 10 minutes with 100 g., 50 g. and 25g., respectively, of the formulated preparations for 100 kg. of seedgrains and sown after 24 hours in lots of 2 m? each with 4 repetitions.

TABLE 2 Infestation of panicles in percent with concentrations of g. ofpreparation for 100 kg. of seed grains Preparation 100 g./100 kg. 50g./100 kg. 25 g./100 kg.

EXAMPLE 3 Cotton seed strongly infested with Rhizoktonia solani wastreated with a preparation A containing as active substance acombination of 10 parts3,3,4,4-tetrachlorotetrahydrothiophene--l,l-dioxide with 60 partsN-trichloromethylmercaptotetrahydrophthalimide (captan) in addition to30 parts talcum as carrier material.

For comparison there were used a preparation B containing as activesubstance parts 1 3,3,4,4-tetrachlorotetrahydrothiophene-l,l-dioxidealone in addition to 80 parts talcum and a preparation C containing 30parts talcum as inert material and 70 partsN-trichloroethylmercaptotetrahydrophthtalimide (captan) as activesubstance.

A commercial seed protectant D containing 2% of mercury was also usedfor comparison.

The formulated preparations were used in concentrations of 400 g., 200g. and 100 g., respectively, for 100 kg. of seed grains. The treatmentlasted 10 minutes. The seed grains were sown in a hot-house in pots withsix repetitions and the result was ascertained by the number of thesound plants that had germinated.

The result so obtained is indicated in the following Table 3. The tableshows that combination A of the invention has a considerably improvedaction as compared with all the comparison preparations includingmercury seed protectant D.

TABLE 3 Percent of germinated sound plants with concentrations of g. ofpreparation for 100 kg. of seed grains Preparation 400 g./100 kg. 200g./100 kg. 100 g./100 kg.

EXAMPLE 4 Winter rye seeds naturally infested to a high degree withFusarium nivale was treated with a preparation A containing as activesubstance a combination of 10 parts3,3,4,4-tetrachlorotetrahydrothiophene- 1,1-dioxide and 20 partshexachlorobenzene in addition to 70 parts talcum as inert material.

Higher concentrations cause too much damage to the plants.

For comparison, there were used a preparation B which contained asactive substance 20 parts 13,3,4,4-tetrachlorotetrahydrothiophenedioxide alone and parts talcum asinert material and a preparation C containing as active substance 30parts hexachlorobenzene alone and 70 parts talcum as inert material.

A commercial seed protectant D containing 2% of mercury was also used ascomparison preparation.

The formulated preparations were used in concentrations of 100 g., 50 g.and 25 g., respectively, for 100 kg. of seed grains. The treatmentlasted 10 minutes.

24 hours after the treatment, the treated seed grains were sown ingermination boxes with sterile garden mould with eight repetitions, eachcomprising 100 seed grains, and then caused to germinate under optimuminfestation conditions in an air-conditioned room at a temperature of 5to 8 C. and to of relative atmospheric moisture.

The evaluation of the experiment is set forth in the following Table 4.The table shows that the effectiveness of combination A is considerablyhigher than that of the individual components B and C and reaches thatof the mercury seed protectant D.

This result is very surprising since the component hexachlorobenzene isalmost ineffective against Fusarium when used alone, as can be seen fromthe table.

TABLE 4 Percent of infestation with Fusarlum with concentrations of g.of preparation ior 100 kg. of seed grains Preparation 10o g./l00 kg. 50g./l00 kg. 25 g./l00 kg.

0 1. 2 a. 5 2. 7 s. 9 15. 4 29. 1 35. o 40. s o. 1 o. s 2. a 63 51. 7as. 4

EXAMPLE 5 Winter rye seeds naturally infested to a high degree withFusarium nivale were treated with a preparation A containing as activesubstance a combination of 5 parts3,3,4,4-tetrachlorotetrahydrothiophene- L l-dioxide and 40 partstetrachloronitrobenzene in addition to 55 parts talcum as inertmaterial.

For comparison there were used a preparation B contaming as activesubstance 20 parts 1 3,3,4,4-tetrachlorotetrahydrothiophene- 1,1-dioxidealone in addition to 80 parts talcum as insert material and apreparation C containing as active substance 45 partstetrachloronitrobenzene alone in addition to 55 parts talcum as inertmaterial.

A commercial seed protectant D containing 2% of mercury was also used ascomparison preparation.

The formulated preparations were applied in concentrations of 100 g., 50g. and 25 g., respectively, for 100 kg. of seed grains.

One day after the treatment the seed grains were sown in the usualgermination boxes filled with sterile garden mould and caused togerminate under optimum infestation conditions in an air-conditionedroom at a temperature of 5 to 8 C. and a relative atmosphere mositure of90 to 100%.

Higher concentrations cause too much damage to the plants.

TABLE 5 Percent of infestation with Fusarium with concentrations of g.of preparation for 100 kg. of seed grain Preparation 100 g./100 kg. 50g./100 kg. 25 g./100 kg.

EXAMPLE 6 Oats artificially infested with Ustilago avenge were treatedwith a preparation A containing as active substance 10 parts3,3,4,4-tetrachlorotetrahydrothiophene-1,1-

dioxide with 10 parts pentachloronitrobenzene and 30 partshexachlorobenzene in addition to 50 parts talcum as inert material.

For comparison there were used a preparation B containing as activesubstance 20 parts 1 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-

dioxide alone in addition to 80 parts talcum as insert material and apreparation C containing as active substance 15 partspentachloronitrobenzene together with 35 parts hexachlorobenzene inaddition to 50 parts talcum.

The seed grains were treated in usual manner for 10 minutes in aconventional drum. Each formulated preparation was applied in aconcentration of 300 g., 200 g., 100 g. and 50 g., respectively, for 100kg. of seed grains. The seed grains were sown in a hot-house in boxesfilled with earth, with four repetitions, each comprising 100 seedgrains. On harvesting, the test was evaluated and the numbers of soundpauicles and infested panicles were determined.

The test result indicated in the following Table 6 shows that the activesubstance combination A in accordance with the invention has aconsiderably improved action against Ustilago avenae in comparison withthat of comparison preparations B and C.

TABLE 6 Infestation o1 panicles with Ustilago avenue in percent with g.of preparation for 100 kg. of seed grains Preparation 300 g./100 kg. 200g./100 kg. 100 g./100 kg. 50 g./100 kg.

Untreated 60. 5 57. 3 54. 6 62. 4

EXAMPLE 7 Cotton seed infested with Rhizoktonz'a solqm' was treated witha preparation A containing an active substance combination of Forcomparison, there were used a preparation B containing as activesubstance Higher concentrations cause too much damage to the plants.

20 parts 1 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-

dioxide and parts talcum as inert material and a preparation Ccontaining as active substance combination 25 partsN-trichloromethylmercaptotetrahydrophthalimide with 30 partstetramethylthiuramdisulfide and 45 parts talcum as inert material.

Seed grains were treated for 10 minutes in a drum. For 100 kg. of seedgrains 400 g., 200 g., 1 00 g., and 50 g., respectively, of theformulated preparations were used. The seed grains were then sown in ahot-house in boxes filled with earth with four repetitions, eachcomprising 100 seed grains. The percentage of sound plants is indicatedin the following Table 7. The table shows to which extent infestationcould be prevented by treatment with the difierent active substancecombinations. The combination of preparation A was most eifective.Preparation B was considerably less eifective and preparation C wasstill less efiective.

TABLE 7 Percent of germiuatedsound plants with concentrations of g. ofpreparation for 100 kg. of seed grains Preparation 400 g./100 kg. 200g./100 kg. 100 g./100 kg. 60 g./10O kg.

Untreated 40. 7 41. 2 39. 8 38. 2

EXAMPLE 8 Winter rye naturally infested with Fusarium nivale was treatedwith a preparation A containing as active substance a combination of (a)5 parts 3,3,4,4 tetrachiorotetrahydrothiophene 1,1-

dioxide with 30 parts manganese-(II)-ethylene-bis-dithiocarbamate and 65parts talcum as inert material.

(b) There was also used a preparation B containing, in-

stead of manganese-(II)-ethylene-bis-dithiocarbamate, 30 partszinc-(II)-ethylene-bis-dithiocarbamate, While otherwise having the samecomposition as preparation A.

For comparison there were used a preparation C containing as activesubstance 20 parts 1 3,3,4,4 tetrachlorotetrahydrothiophene-1,l-dioxidealone in addition to 80 parts talcum as inert material and a preparationD containing as active substance 35 parts manganese(II)-ethylene-bis-dithiocarbamate alone in addition to 65 parts talcumand furthermore a preparation E containing as active substance 35 partszinc-(II)-ethyleue-bis-dithiocarbamate alone and 65 parts talcum asinert material.

The formulated preparations were used in concentrations of 200 g., 100g., 50 g. and 25 g., respectively, for 100 kg. of seed grains. Thetreatment lasted 10 minutes.

24 hours after the treatment, the seed grains were sown in boxes filledwith sterile garden mould with four repetitions, each comprising 100seed grains and then caused to germinate under optimum infestationconditions in an air-conditioned room at a temperature of 5 to 8 C. andto of relative atmospheric moisture.

Higher concentrations cause too much damage to the plants.

7 The result indicated in the following Table 8 shows that activesubstance combinations A and B in accordance with the invention areessentially more elfective than the individual components.

TABLE 8 Percent of infestation with Fusarium with concentrations of g.of preparation for 100 kg. of seed grains Oats strongly infested withHelminthosporium ave/lac was treated with a preparation A containing asactive substance a combination of 8 parts3,3,4,4-tetrachlorotetrahydrothiophene-1,l-dioxide with 20 partsmanganese-(II)-ethylene-bis-dithiocarbamate and 72. parts talcum asinert material.

There was also used a preparation B containing as active substancezinc-(II)-ethylene-bis-dithiocarbamate instead ofmanganese-(II)-ethylene-bis-dithiocarbamate, while otherwise having thesame composition.

For comparison there were used a preparation C containing 20 parts 13,3,4,4, tetrachlorotetrahydrothiophene 1,1-

dioxide alone as active substance in addition to 80 parts talcum asinert material and a preparation D containing 28 parts manganese (II)ethylene-bis-dithiocarbamate alone as achieve substance in addition to72 parts talcum as inert material and furthermore a preparation Econtaining 28 parts zinc-(II)-ethylene-bis-dithiocarbarnate alone asactive substance in addition to 72 parts talcum as inert material.

The formulated preparations were used in concentrations of 300 g., 200g., 100 g. and 50 g., respectively, for 100 kg. of seed grains. Thetreatment lasted 10 minutes.

Percent of infestation with Hclminthosporium avenue with concentrations01 g. of preparation for 100 kg. oi seed grains Preparation 300 g. 200g. 100 g. 60 g.

EXAMPLE 10 Oats artificially infested with Ustilago avenae were treatedwith a preparation A having the following composition Higherconcentrations cause too much damage to the plants.

10 parts 3,3,4,4 tetrachlorotetrahydrothiophene 1,1-

dioxide with 10 parts pentachloronitrobenzene and 30 partsmanganese-(II)-ethylene-bis-dithiocarbamate in addition to 50 partstalcum as inert material.

For comparison, there were used a preparation B containing as activesubstance 20 parts 1 3,3,4,4 tetrachlorotetrahydrothiophene l,l-

dioxide alone in addition to parts talcum as inert material and apreparation C containing 15 parts pentachloronitrobenzenc together with35 parts manganese-(II)-ethylene-bis-dithiocarbamate in addition to 50parts talcum as inert material.

The seed grains were treated for 10 minutes in usual manner in aconventional drum. The formulated preparations were used inconcentrations of 300 g., 200 g., g. and 50 g., respectively, for 100kg. of seed grains. The seed grains were sown in boxes filled with earthin a hothouse with four repetitions, each comprising 100 seed grains. Onharvesting, the comparison was evaluated and the numbers of soundpanicles and infested panicles were determined.

The test result indicated in the following Table 10 shows that theactive substance combinations in accordance with the invention have aconsiderably improved action against Ustilago avenae in comparison withthat of the individual components.

TABLE 10 Percent of panicles infested with Uatilago avenue with Weclaim:

1. Composition of matter consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,1- dioxide in a ratio by weight withinthe range of 1:1 to 1:10 with a member of the group consisting ofpentachloronitrobenzene, tetrachloronitrobenzene,tetramethylthiuramdisulfide and the manganous salt ofethylene-bis-dithioca-rbamic acid.

2. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,1-dioxide with pentachloronitrobenzenein a ratio by weight within the range of 1:1 to 1:10.

3. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,l-dioxide with tetrachloronitrobenzenein a ratio by weight within the range of 1:1 to 1:10.

4. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,l-dioxide with hexachlorobenzene in aratio by weight of about 1:2.

5. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-l,l-dioxide withtetramethylthiurarndisulfide in a ratio by weight within the range of1:1 to 1:10.

6. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,l-dioxide with Ntrichloromethylmercaptotetrahydrophthalimide in a ratio by weight ofabout 1:6.

7. Composition consisting essentially of a mixture of 3.3.4.4tetrachlorotetrahydrothiophene-1,l-dioxide with hexachlorobenzene andpentachloronitrobenzene in a ratio by weight of about 1:3: 1.

Higher concentrations cause too much damage to the plants.

8. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,1-dioxide withtetramethylthiuramdisulfide and Ntrichloromethylmercaptotetrahydrophthalirnide in a ratio by Weight ofabout 1:6:4.

9. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,1-dioxide withmangan-ous-ethylene-bis-'dithiocarbamate in a ratio by Weight Within therange of 1:1 to 1:10.

10. Composition consisting essentially of a mixture of 3,3,4,4t'etrachlorotetrahydrothiophene-1,1-dioxide with manganous ethylene bisdithiocarbamate and pentachloronitrobenzene in a ratio by weight ofabout 1:3:1.

11. Composition consisting essentially of a mixture of 3,3,4,4tetrachlorotetrahydrothiophene-1,l-dioxide with zinc (II)ethylene-bis-dithiocarbamate in a ratio by weight of about 1:25 to 1:6.

12. Seed protectant composition containing, in addition to an inertcarrier material, a mixture of (A)3,3,4,4-tetrachlorotetrahydrothiophene 1,1-dioxide with (B)pentachloronitrobenzene, tetrachloronitrobenzene,tetramethylthiurarndisulfide or manganous ethylene-bis-dithiocarbamate,components A and B being present in a weight ratio of 1:1 to 1:10.

13. A method of protecting seeds comprising applying to said seeds acomposition as defined in claim 12.

References Cited UNITED STATES PATENTS 2,957,887 10/1960 Berkey 260-3321OTHER REFERENCES Frear, Pesticide Index (1961), 1st ed., p. 175. Frear,Pesticide Index (1963), 2nd ed., pp. 47, 142, 155, 181, 214 and 226-227.

ALBERT T. MEYERS, Primary Examiner S. J. FRIEDMAN, Assistant ExaminerUS. Cl. X.R.

